WO2020153532A1 - Revêtement céramique pour empêcher la corrosion d'un matériau en aluminium ayant des caractéristiques de surface améliorées - Google Patents

Revêtement céramique pour empêcher la corrosion d'un matériau en aluminium ayant des caractéristiques de surface améliorées Download PDF

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WO2020153532A1
WO2020153532A1 PCT/KR2019/005459 KR2019005459W WO2020153532A1 WO 2020153532 A1 WO2020153532 A1 WO 2020153532A1 KR 2019005459 W KR2019005459 W KR 2019005459W WO 2020153532 A1 WO2020153532 A1 WO 2020153532A1
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coating
coating layer
silica
weight
primer
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English (en)
Korean (ko)
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남유준
김상목
김민희
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주식회사 네오플램
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres

Definitions

  • the present invention is a first step of coating the coated surface of a product of aluminum material with a primer coating solution containing silica particles and graphene; And a second step of coating with a silica coating solution further containing cellulose nanofibers (CNFs), a corrosion-resistant coating method comprising a coating method for preventing corrosion of aluminum materials with reduced surface defects, and a coating layer introduced accordingly. It relates to an improved cookware made of aluminum.
  • Kitchen utensils such as frying pans and pots have been mainly produced using materials such as ordinary steel, aluminum alloy, aluminum plate, and stainless steel.
  • materials such as ordinary steel, aluminum alloy, aluminum plate, and stainless steel.
  • aluminum materials that are light yet easy to mold and are inexpensive to manufacture are often used.
  • aluminum is attracting attention as a material for cooking utensils because it is light, has excellent thermal conductivity and has no toxicity.
  • the devices made of these materials exhibit many problems, such as repeated metal expansion and contraction due to rapid heating and rapid cooling, damage and oxidation, peeling, and corrosion of the coated surface due to consumer negligence.
  • the metal component such as aluminum is exposed due to the coating being peeled off, and the substrate is corroded due to the acid component of the cooking by sticking food and food to the portion where the coating is peeled off. It has been reported to accumulate and cause side effects such as Alzheimer's disease.
  • the kitchen tool has a high corrosion resistance and resistance to peeling and scratch resistance while being able to withstand high cooking temperatures, and does not stick to food.
  • the kitchen surface of the product is coated with fine ceramics using inorganic paints and inorganic ceramic coating compositions that have properties such as excellent heat resistance, contamination resistance, chemical resistance, and durability. Techniques have been used to prevent metal corrosion of instruments.
  • ceramics traditionally use natural raw materials such as clay, and have been used as a container (porcelain). Recently, it is a term that collectively refers to products that have been heat-treated using high-purity artificial inorganic materials such as glass and metal oxide, and is called fine ceramics to distinguish them from ceramics.
  • Ceramic coating is a fine ceramic with strong corrosion resistance, heat resistance, and abrasion resistance.
  • the ceramic coating is applied to the surface of the product to prevent corrosion of metal and prevent food from sticking during cooking. have.
  • Ceramic-coated kitchen containers can implement various colors that are difficult to express with other coatings such as fluorine coatings, and the coatings do not come off or burn even at temperatures above 350°C, as well as many advantages such as non-toxic, anti-bacterial, and far-infrared rays from natural minerals.
  • fluorine coatings such as fluorine coatings
  • advantages such as non-toxic, anti-bacterial, and far-infrared rays from natural minerals.
  • peel off due to the short persistence of food non-stickiness (nonstick, non-stick) and properties weak to impact. Additional processing is required.
  • the inventors of the present invention have improved surface properties, while blocking the peeling and/or cracking of the coating layer, and at the same time exerting efforts to discover a method of introducing a coating layer capable of imparting corrosion resistance, as a result of silica precursor having an average diameter of 10 nm or less and final After primary coating with a primer coating solution containing 0.3 to 2% by weight of graphene based on the weight of the composition, a CNF-containing ceramic coating layer further comprising cellulose nanofibers in the existing ceramic coating on the primary coating layer By forming, the surface properties were improved, and peeling and/or cracking of the coating layer was blocked, and it was confirmed that it was possible to provide a kitchen utensil with an aluminum material with improved corrosion resistance.
  • One object of the present invention is to coat the coated surface of a product made of aluminum with silica particles and final.
  • Another object of the present invention is an aluminum substrate; A primer coating layer formed on the aluminum substrate from a coating solution containing silica precursor having an average diameter of 10 nm or less in particle size and 0.3 to 2% by weight of graphene based on the weight of the final composition; And a ceramic coating layer formed on the primer coating layer from a silica coating solution containing silica sol, silane, oxide and 0.5 to 3% by weight of cellulose nanofibers (CNF) in a solvent, an aluminum material with improved corrosion resistance Is to provide cookware
  • CNF cellulose nanofibers
  • the coating method of the present invention is an aluminum material that is vulnerable to chlorine-containing corrosives by blocking the inflow of a caustic agent because the strength is enhanced and the surface properties are improved, i.e., there are no cracks and there are few micropores to form a smooth surface coating layer with low surface roughness.
  • FIG. 1 is a schematic diagram of a ceramic coating layer according to an embodiment of the present invention.
  • FIG. 2 is a view showing the stability of a primer coating solution containing graphene according to an embodiment of the present invention.
  • Figure 3 is a diagram showing the stability of the solution according to the concentration of methyltrimethoxysilane (methyltrimethoxysilane; MTMS) used as a silane-based compound.
  • MTMS methyltrimethoxysilane
  • FIG. 4 is a diagram showing a step-by-step method of manufacturing a coating solution according to an embodiment of the present invention.
  • FIG. 5 is a view showing the corrosion resistance of the brine of the ceramic coating layer according to an embodiment of the present invention introduced on an aluminum substrate.
  • FIG. 6 is a view showing the corrosion resistance of CuCl 2 of the ceramic coating layer according to an embodiment of the present invention introduced on an aluminum substrate.
  • FIG. 7 is a view showing a crack resistance (crack) of the ceramic coating layer according to an embodiment of the present invention introduced on an aluminum substrate.
  • FIG 8 is a view showing a microporous reduction on the surface of a ceramic coating layer according to an embodiment of the present invention introduced on an aluminum substrate.
  • the present invention provides a silica particle and a final coated surface of an aluminum material product.
  • CNF cellulose nanofiber
  • the present invention introduces a ceramic coating layer for preventing corrosion in manufacturing a kitchen appliance based on an aluminum material, but further contains CNF in the coating solution, thereby reducing surface defects, roughness and/or pores to a smooth surface. It is based on the discovery of a coating method capable of imparting excellent corrosion resistance by forming and improving cracks due to an increase in the thickness of the coating layer, which is a problem occurring in the ceramic coating layer that does not include it. Furthermore, prior to introducing the ceramic coating layer, by forming a primer coating layer further comprising graphene, it not only exhibits synergistic corrosion resistance, but also proposes a coating method capable of improving peeling durability by improving adhesion with the ceramic coating layer.
  • the "graphene” contained in the primer coating solution of the present invention is one of the carbon allotropes and has a structure made of an atomic honeycomb lattice, and is also used as a water treatment filter for desalination. This can impart corrosion resistance to block the penetration of chlorine ions, and also increase the strength of the coating layer through a plate-like structure, while at the same time inhibiting the movement of the corrosive agent, it can exhibit a synergistic effect on corrosion resistance.
  • the primer coating solution and / or ceramic coating material is an inorganic particle having a particle size of 5 to 15 ⁇ m; And it may include a coating composition comprising water.
  • the inorganic particles may be 3 to 10% by weight of the total content, the inorganic particles are alumina, silica, zirconia, silicon carbide, titanium carbide, aluminum It may be one or more selected from boride (aluminum boride) and cristobalite (cristobalite), in particular alumina or silica, but is not limited thereto.
  • the primer coating solution is prepared by mixing tetraethyl orthosilicate (TEOS), a water-containing solvent, and nitric acid to prepare a silica precursor having an average particle size of 10 nm or less; Step 1-2 of reacting by adding a mixed solution of methyltrimethoxysilane (MTMS) and isopropyl alcohol to the silica precursor solution; And the first to third steps of adding and dispersing graphene in an amount of 0.3 to 2% by weight based on the weight of the final composition in the solution obtained from the first and second steps; but it is not limited thereto.
  • TEOS tetraethyl orthosilicate
  • MTMS methyltrimethoxysilane
  • isopropyl alcohol isopropyl alcohol
  • the first and second steps may be performed by further including polydimethylsiloxane, polysilazane, or both, but are not limited thereto.
  • a silica precursor having a particle size prepared from TEOS, a water-containing solvent, and an acid catalyst is adjusted to an average diameter of 10 nm or less.
  • TEOS used as a precursor is a material suitable for producing a small sized silica precursor having a stable network structure and a high specific surface area. Therefore, the coating method of the present invention using TEOS as a precursor has a lower surface roughness (roughness) of the formed coating layer compared to the use of silica sol containing relatively large particles with an average diameter of 12 to 80 nm rather than TEOS, Defects such as pinholes can be prevented. Since a corrosion agent is introduced into the pinhole to cause corrosion on the surface to be coated, the coating layer having reduced pinhole formation using the coating method of the present invention may contribute to increase corrosion resistance.
  • the step of preparing a silica precursor from the TEOS is performed by a sol-gel method through hydrolysis and condensation reaction under water and an acid catalyst, thereby adding flexibility to the surface by adding methyl trimethoxysilane (MTMS). It can exhibit the effect of improving the corrosion resistance to the corrosion agent by hydrophobicizing locally, while improving the adhesion with the ceramic coating layer introduced on the primer coating layer.
  • MTMS methyl trimethoxysilane
  • nitric acid As the acid catalyst, it is preferable to use nitric acid as the acid catalyst.
  • an organic acid such as formic acid other than nitric acid
  • nitric acid can improve stability so that it can be evenly dispersed by improving repulsion by changing the interaction between nanoparticles by changing the electric field of the particle surface even with a small change in pH.
  • the primer coating solution is based on forming a silica precursor by sol-gel method through hydrolysis and condensation reaction of TEOS. Therefore, it is necessary to contain a certain amount of water or more in a solvent for hydrolysis. For example, when considering the reaction equivalent, the amount of water contained in the solvent is preferably 4 times the molar concentration of the silica precursor mixture. However, in consideration of the occurrence of variables such as loss during synthesis, it may be contained in a sufficient amount of 4 times or more molar concentration, but is not limited thereto.
  • the coating method of the present invention may further include a third step of coating with a top coat coating solution containing silica sol and silane.
  • the top coat coating solution may further include additives used in the top coat coating solution of cookware in the art in addition to silica sol and silane, but is not limited thereto.
  • the third step may be performed by a spray coating method, or may be performed without limitation using a coating method applicable to common cooking utensils known in the art.
  • the MTMS content in the final primer solution can be 5 to 20% by weight relative to the weight of the final composition.
  • the content of MTMS exceeds 20% by weight, precipitation may occur by overreaction with the TEOS precursor, and the degree of hydrophobicity of the primer coating solution to be produced increases, thereby coating a water-soluble coating on the top of the surface. It does not spread evenly and can cause bunching.
  • a solvent containing C 1-4 alcohol may be used as a solvent for the silica coating solution, but is not limited thereto, and a solvent used in a coating solution of a conventional cooking utensil may be used without limitation.
  • the silane contained in the silica coating solution may be vinyltriethoxysilane, epoxyglycan (3-glycidoxypropyltrimethoxysilane), phenyltriethoxysilane, dimethyldimethoxysilane, or a mixture thereof. However, it is not limited thereto.
  • the oxide contained in the silica coating solution may be silicon dioxide, alumina, zirconium oxide, mica, or a mixture thereof.
  • a mixture of silicon dioxide and alumina can be used, but is not limited thereto.
  • the silica coating solution may further include a pigment for color expression, but is not limited thereto.
  • a pigment usable to express the color of the cooking utensil may be used without limitation.
  • the primer coating layer and the ceramic coating layer formed from the first step and the second step have a thickness of 35 ⁇ m or more
  • CNF in the second step without the primer coating layer formed to the same thickness It may be that the cracks on the surface is reduced compared to the coating prepared by not including.
  • a composition having two or more CNF-free or non-CNF coatings is prepared to form a primer coating layer, a CNF-containing ceramic coating layer, and a topcoat coating layer, or a CNF-free ceramic coating layer without a primer coating layer.
  • a top coat layer was formed on the coating to a thickness of 35, 40, and 45 ⁇ m, and the microstructure of the surface was confirmed. As a result, a microcracking began to be observed from the 35 ⁇ m thickness of the CNF-free coating, increasing to 45 ⁇ m thickness. Although the degree of cracking gradually increased, it was confirmed that in the case of a coating containing CNF, no crack was observed even when the thickness was increased to 35 ⁇ m as well as 45 ⁇ m.
  • the final manufactured coating according to the present invention has a size of 200 to 400% reduced in the size of micropores formed on the surface, and a total area of 700 to 800% of reduced micropores compared to a coating prepared without CNF in the second step. It is characteristic.
  • the present invention is an aluminum substrate; A primer coating layer formed on the aluminum substrate from a coating solution containing silica precursor having an average diameter of 10 nm or less in particle size and 0.3 to 2% by weight of graphene based on the weight of the final composition; And a ceramic coating layer formed on the primer coating layer from a silica coating solution containing silica sol, silane, oxide, and cellulose nanofiber (CNF) in a content of 0.5 to 3% by weight in a solvent, an aluminum material with improved corrosion resistance Provides cookware.
  • a coating solution containing silica precursor having an average diameter of 10 nm or less in particle size and 0.3 to 2% by weight of graphene based on the weight of the final composition
  • a ceramic coating layer formed on the primer coating layer from a silica coating solution containing silica sol, silane, oxide, and cellulose nanofiber (CNF) in a content of 0.5 to 3% by weight in a solvent, an aluminum material with improved corrosion resistance Provides cookware.
  • Solvents, silica sol, silane, and oxides usable in the silica coating solution are as exemplified in the coating method.
  • the thickness of the coating layer in the cooking utensil of the present invention may be 20 to 50 ⁇ m.
  • the coating layer may be a thickness of a primer coating layer and a ceramic coating layer, or may include a thickness including all of a top coating layer formed in a thickness of 10 to 15 ⁇ m on the ceramic coating layer, but is not limited thereto.
  • the thickness of the coating layer may be determined in consideration of the type, shape, and/or purpose of use of the product to be applied.
  • the cooking utensil of the present invention may have an increased strength and improved corrosion resistance compared to a product not containing graphene in the primer coating layer.
  • the cooking utensils of the present invention may be improved in resistance to various caustic agents, such as caustic agents such as acid, brine, alkali, and specifically, chlorine-containing caustic agents, but is not limited thereto.
  • caustic agents such as acid, brine, alkali, and specifically, chlorine-containing caustic agents, but is not limited thereto.
  • the ceramic coating layer of the present invention significantly reduces the size and/or frequency of micropores formed on the surface by further including CNF in a paint constituting the existing ceramic coating layer.
  • the ceramic coating of the present invention does not crack even if the thickness increases to 50 ⁇ m. Therefore, peeling due to peeling of the coating layer through the micropores and/or cracks and the inflow of the corrosive agent through them can be significantly reduced, thereby effectively preventing corrosion of the aluminum substrate by the inflow of the corrosive agent.
  • each component is expressed as a weight percent based on the total weight of the final primer coating liquid composition.
  • 41% by weight of tetraethoxysilane tetraethoxysilane or tetraethyl orthosilicate; TEOS
  • TEOS tetraethoxysilane or tetraethyl orthosilicate
  • MTMS methyltrimethoxysilane
  • IPA isopropyl alcohol
  • a solution was prepared, added to the TEOS precursor solution, and stirred at room temperature for 1 hour to prepare a silica precursor.
  • 1% by weight of graphene was added and stirred for 1 hour to evenly disperse.
  • the obtained graphene-containing primer coating solution was photographed and shown in FIG. 2.
  • the graphene-containing primer coating solution exhibited high stability to maintain a uniformly dispersed graphene without phase separation or precipitation.
  • CNF cellulose nanofiber
  • an alcohol solvent with silica sol, pigment, silicon dioxide, alumina and other additives and then basket milled at 1000 rpm for 2 hours (total 55 to 65% by weight relative to the final composition)
  • a methyl trimethoxysilane (30 to 45% by weight) hydrolyzed with formic acid or acetic acid was mixed to prepare a ceramic paint (base coat) containing CNF.
  • Step 1 Formation of the primer coating layer
  • Step 2 Formation of ceramic coating layer (undercoat)
  • the CNF-containing ceramic paint prepared according to Example 2 was coated on the upper surface.
  • the temperature of the substrate was adjusted to 50 to 55°C, and the thickness of the coating layer including the primer coating layer and the ceramic coating layer was 25 to 30 ⁇ m.
  • a top coat coating layer having a thickness of 10 to 15 ⁇ m was further formed by a conventional method using a functional top coat solution composed of silica sol and silane.
  • Example 3 To check the corrosion resistance of the test product prepared according to Example 3 and the comparative product (Comparative Example 1) prepared by the conventional coating method, after washing the surface of the prepared product with a neutral detergent and lukewarm water, 10 weight The NaCl aqueous solution of% concentration was filled to a height of 3 cm and the temperature of the aqueous solution was maintained at a boiling temperature for 2 hours. However, the salt concentration was maintained by replenishing water in an amount reduced by evaporation during heating. Thereafter, the aqueous solution of NaCl was removed and left for 22 hours to observe the degree of corrosion on the surface. The above process was defined as one cycle, and a total of 15 cycles were repeated.
  • the ceramic coating layer was introduced on the aluminum substrate by spray coating by a continuous process according to steps 1 and 2 of Example 3 while controlling the temperature of the substrate to 60 to 65°C and 50 to 55°C, respectively. Furthermore, after introducing the top coat layer according to step 3, three samples were prepared by adjusting the total thickness to 35, 40 and 45 ⁇ m, including the final top coat layer, and confirming whether or not cracks on the surface were generated by an optical microscope. It is shown in FIG. 7. To observe fine cracks, a black ink was evenly applied to the surface, followed by washing with alcohol to prepare a sample. Magnification was used 200 times. As shown in FIG.
  • micropores are generated on the surface of the coating layer while spraying the ceramic solution and the solvent evaporates, which causes cracks, and the introduction of the corrosion medium through the cracks may cause corrosion of the product and peeling of the coating layer.
  • Microporous properties on the surface of the coating layer were analyzed at 10000 magnification through SEM, and the results are shown in FIG. 8. The size and area of the micropores were analyzed from the images obtained using an image analysis program (Image J). As shown in FIG.
  • the size of the micropores observed on the surface of the coating layer of the product coated with the ceramic layer containing CNF according to the manufacturing method of the present invention was reduced by about 300% compared to the product produced by the conventional coating method, The total area of pores was reduced by about 750%. Further, in the case of a product manufactured by the conventional coating method, significant cracking of the coating layer was observed, but in the product coated with a ceramic layer containing CNF according to the manufacturing method of the present invention, crack generation was significantly reduced.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Nanotechnology (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
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Abstract

La présente invention concerne un procédé de revêtement pour empêcher la corrosion d'un matériau en aluminium ayant des irrégularités de surface réduites, et un ustensile de cuisine qui est fabriqué à partir d'un matériau en aluminium ayant une résistance à la corrosion améliorée et qui comprend une couche de revêtement introduite par celui-ci, le procédé comprenant : une première étape de revêtement, avec une solution de revêtement d'apprêt comprenant des particules de silice et du graphène, une surface à revêtir d'un produit fabriqué à partir d'un matériau en aluminium ; et une seconde étape d'application d'une solution de revêtement de silice comprenant en outre des nanofibres de cellulose (CNF).
PCT/KR2019/005459 2019-01-21 2019-05-08 Revêtement céramique pour empêcher la corrosion d'un matériau en aluminium ayant des caractéristiques de surface améliorées WO2020153532A1 (fr)

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KR1020190007761A KR102152404B1 (ko) 2019-01-21 2019-01-21 표면 특성이 개선된 알루미늄 소재의 부식 방지용 세라믹 코팅

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CN115321992A (zh) * 2022-09-06 2022-11-11 哈尔滨工业大学 一种GNPs/YSZ复合陶瓷粉体及其制备方法和应用
CN115466531A (zh) * 2022-10-19 2022-12-13 深圳前海石墨烯产业有限公司 去除羰基氧化石墨烯陶瓷涂料及其制备方法和用途

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KR102516574B1 (ko) * 2020-12-04 2023-03-31 휴켐플러스 주식회사 무기 세라믹 차열 방수 바닥 코팅제 제조방법 및 제조한 코팅제를 사용하는 바닥 코팅방법
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CN115466531A (zh) * 2022-10-19 2022-12-13 深圳前海石墨烯产业有限公司 去除羰基氧化石墨烯陶瓷涂料及其制备方法和用途
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